CN115948097B - Moisture-heat resistant epoxy powder composition for magnetic ring and preparation method and application thereof - Google Patents
Moisture-heat resistant epoxy powder composition for magnetic ring and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a moisture-heat resistant epoxy powder composition for a magnetic ring, which comprises the following components: epoxy resin 1, epoxy resin 2, epoxy resin 3, imidazole curing agent, filler, inorganic flame retardant, solid organic phosphorus flame retardant, melamine borate, zirconium phosphate flame retardant, adhesion promoter 1, adhesion promoter 2, titanium pigment, flatting agent, degasifying agent and external thixotropic agent. The epoxy powder composition of the invention can be mainly used for insulating protection of magnetic rings (iron-silicon-aluminum, iron-based amorphous strips, iron powder cores, manganese cores, nickel cores and the like) made of various materials, and meets the process conditions of 190-230 ℃ preheating coating and 200 ℃/(5-10) minute curing. And the method can also be applied to insulation protection of electronic elements such as bus bars, rotors, stators, polymer fuses (PPTC) and the like.
Description
Technical Field
The invention belongs to the technical field of electronic component packaging materials, and particularly relates to a damp-heat resistant epoxy powder composition for a magnetic ring, and a preparation method and application thereof.
Background
The powder coating consists of solid resin, curing agent, pigment, filler, auxiliary agent and other components, is a low-VOC solid coating, is applied to the surface of a substrate by electrostatic spraying or fluidized bed coating method, and has the characteristics of environment friendliness, high efficiency and the like. The powder coating for electrical insulation is an important branch of the powder coating and is mainly applied to the aspect of insulation protection of electronic components.
The magnetic ring is an annular magnetizer, is commonly used as an anti-interference element in an electronic circuit, is widely used in the fields of electric power, electronics, data communication equipment and the like, has high requirements on electric insulation performance and high voltage breakdown resistance, and needs to carry out insulation protection and mechanical protection on the surface coating of the magnetic ring. Common magnetic ring materials are Fe-Si-Al, fe-based amorphous strips, iron powder cores, manganese cores, nickel cores, and the like. The metal soft magnetic powder core used for the magnetic ring is powder made of metal or alloy soft magnetic materials, is formed by pressing the powder through a pressing machine after insulation and cladding treatment, has uniformly distributed air gaps, can effectively reduce eddy current loss, and can meet the electrical property requirement after high-temperature sintering of the pressed product.
One of the main problems of the prior magnetic ring coated with the electric insulation powder coating is insufficient resistance to damp and hot environment, and after long-time storage at high temperature and high humidity, the coating falls off and bulges from the surface of the magnetic ring, and when the magnetic ring encounters high voltage, transient breakdown occurs, so that the insulation layer is damaged and fails.
At present, the insulating powder coating for the magnetic ring is searched for a number of related patents as follows:
1. an epoxy resin powder coating for coating magnetic rings and a preparation method thereof (authority publication No. CN 103059692B) are provided, wherein high-bromine epoxy resin is introduced into the resin for the first time, so that the flame retardance of the coating is greatly improved. A halogen-free flame-retardant epoxy resin powder coating (application publication No. CN 104745048A) for coating magnetic rings uses an organophosphorus flame retardant and a flame-retardant synergist to meet the U94V-0 requirement. Both patents use phenol resin curing agent and 2-methylimidazole accelerator as curing system, and the two technical schemes can not meet the requirement of 85% high-temperature high-humidity storage for 1000h at 85 ℃. The two patents are essentially different from the present patent.
2. A two-step method low-temperature fast-curing magnetic ring special powder and a preparation method thereof (grant publication No. CN 107674547B), wherein the method of using A, B two components improves the storage stability of the powder, the A component contains dicyandiamide as a curing agent, and the B component contains a derivative of 2-heptadecyl imidazole as a curing accelerator. The dicyandiamide and imidazole derivative combined curing system is tested, and the requirement of 85% high-temperature high-humidity storage for 1000 hours at 85 ℃ cannot be met. This patent differs substantially from the patent of the present invention.
3. An insulating powder paint is prepared from epoxy resin, modified dicyandiamide as solidifying agent, phenol-type phenolic aldehyde solidifying agent, silicate filler and promoter through coating the insulating powder on the microwave ferrite for 5G base station, and features high conductivity, insulating nature, high resistance to dual-85 wet heat, flame retarding and high temp resistance. The patent uses dicyandiamide and phenol type phenolic resin as curing agent, and the accelerator is imidazole substance. The mode of realizing flame retardance of the patent is mainly epoxy resin synthesized by brominated bisphenol A, and has essential difference with non-halogen flame retardant used in the patent.
4. An epoxy powder coating and a preparation method thereof (application publication number CN 110105847A) disclose an epoxy powder coating for coating the surface of an amorphous nanocrystalline magnetic ring, and the coating has the advantages of good insulation effect, high hardness, high curing speed, good flame retardant effect, environmental protection, simple preparation method and the like. The epoxy powder coating comprises the following components: bisphenol A epoxy resin is matched with o-alpha/phenolic epoxy resin, dicyandiamide curing agent, imidazole curing accelerator, aluminum hydroxide, magnesium hydroxide or zinc borate as flame retardant. This patent differs substantially from the patent of the present invention.
5. An electric insulating powder coating for magnetic ring copper bars (application publication number 111234659A), which discloses an electric insulating powder coating for magnetic ring copper bars, mainly comprising the following components: the phenolic aldehyde modified epoxy and bisphenol A epoxy mixture is prepared from amine curing agent and phenolic curing agent, the drier is a mixture of cobalt hydroxide, glycerol and sorbitol, and the flame retardant is a mixture of decabromodiphenylethane, antimony trioxide and melamine cyanurate. The patent flame-retardant system is halogen flame-retardant, does not meet the technical requirement of the current mainstream halogen-free flame retardance, and has essential difference with the patent.
No publications related to the present patent application have been found by search.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a wet-heat-resistant epoxy powder composition for a magnetic ring and a preparation method thereof.
The technical scheme adopted for solving the technical problems is as follows:
the moisture-heat resistant epoxy powder composition for the magnetic ring comprises the following components in parts by weight:
further, the epoxy resin 1 is a solid bisphenol a type epoxy resin, and the softening point is: 60-130 ℃, the epoxy equivalent is: 450-1800g/eq;
or the epoxy resin 2 is solid organic silicon modified epoxy resin;
or the epoxy resin 3 is modified epoxy resin containing phosphate, and the specific preparation method comprises the following steps:
the epoxy phosphate resin prepared by reacting epoxy resin E44 with phosphoric acid has the following reaction formula:
3 parts by weight of epoxy phosphate resin is taken and added into 5 parts by weight of silicon micropowder in a dropwise manner, and the mixture is uniformly mixed by a high-speed mixer at 500-1500rpm for 5-15 minutes; then adding 10 parts by weight of CYD-014, NPES904 or GESR904, uniformly mixing by a high-speed mixer at 500-1500rpm for 5-15 minutes; and then the mixture is melted and extruded by a double-screw extruder, the temperature of the extruder is set to 120-130 ℃, the mixture is crushed by a crusher after being cooled by a cooling press roller, and the mixture is screened by a 100-target standard sieve, so that the epoxy resin 3 can be obtained.
Further, the epoxy resin 1 is E12, NPES907, NPES904, GESR903, CYD-014U, CYD-014 or CYD-012.
Further, the imidazole curing agent is: one or a mixture of imidazole curing agents without masking agent and imidazole curing agents with masking agent, which are coated by wax powder;
the preparation method of the imidazole curing agent without masking agent, which is coated by the wax powder, comprises the following steps:
uniformly mixing 1-2 parts by weight of polyethylene micro powder wax (melting point: 100-130 ℃) and 2-3 parts by weight of imidazole substances without masking agents, wherein the rotating speed is 500-1500rpm, and the mixing time is 5-15 minutes; then the mixture is melted and extruded by a double screw extruder, the temperature of the extruder is set to 120-140 ℃, the mixture is crushed by a crusher after being cooled by a cooling press roller, and the mixture is sieved by a 100-mesh standard sieve, so that the imidazole curing agent which is coated by wax powder and does not contain masking agent is obtained;
the imidazole curing agent with masking agent comprises: 1-cyanoethyl-2-undecylimidazolium-trimellitate (C11Z-CNS), 1-cyanoethyl-2-phenylimidazolium-trimellitate (2 PZCNS), 1-cyanoethyl-2-phenylimidazolium-trimellitate micropowder (2 PZCNS-PW), 2,4' -diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine (2 MZ-A), 2,4' -diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine micropowder (2 MZA-PW), 2,4' -diamino-6- [2' -ethyl-4 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine (2E 4 MZ-A), 2,4' -diamino-6- [2' -undecylimidazolyl- (1 ') ] -ethyl-s-triazine (C11Z-A); 2-phenylimidazole isocyanuric acid adduct (2 PZ-OK), 2,4' -diamino-6- [2' -methylimidazole- (1 ') ] -ethyl-s-triazine isocyanuric acid adduct dehydrate (2 MA-OK), 2-phenyl-4, 5-dihydroxymethylimidazole (2 PHZ), 2-phenyl-4, 5-dihydroxymethylimidazole micropowder (2 PHZ-PW), 2-phenyl-4-methyl-5-hydroxymethylimidazole (2P 4 MHZ), 2-phenyl-4-methyl-5-hydroxymethylimidazole micropowder (2P 4 MHZ-PW).
Further, the imidazole substance without masking agent is 2-methylimidazole (2 MZ), or 2-phenylimidazole (2 PZ), or 2-phenyl-4-methylimidazole (2P 4 MZ).
Further, the filler is one or a combination of more than two of silicon micropowder, talcum powder, mica powder, calcium silicate, zirconium silicate, calcium carbonate, barium sulfate and kaolin;
or the inorganic flame retardant is one or a combination of more than two of aluminum hydroxide, magnesium hydroxide, boehmite and carbonate type aluminum-magnesium hydrotalcite;
or the solid organic phosphorus flame retardant is one or a combination of more than two of solid phosphazenes and solid phosphates;
or, the melamine borate is a synergistic flame retardant;
or the zirconium phosphate flame retardant is one or a combination of two of zirconium phosphate and organically modified zirconium phosphate.
Further, the adhesion promoter 1 is one or a combination of two or more of aluminum tripolyphosphate, modified aluminum tripolyphosphate and aluminum dihydrogen tripolyphosphate;
or the adhesion promoter 2 is one or a combination of two or more of amino-type organosiloxane, epoxy-type organosiloxane and mercapto-type organosiloxane;
or the titanium dioxide is one or a combination of two of rutile titanium dioxide and anatase titanium dioxide;
or the pigment is one or a combination of two or more of phthalocyanine blue, iron red, iron yellow, organic yellow pigment, organic red pigment, organic orange pigment, carbon black and inorganic black pigment;
or the leveling agent is polybutyl acrylate leveling agent;
or the degasifying agent is one or two of benzoin and modified benzoin;
or the externally added thixotropic agent is one or a combination of two of fumed silica and fumed alumina;
further, the amino-type organosiloxane is KH540, the epoxy-type organosiloxane is KH60, and the mercapto-type organosiloxane is KH590; the polybutyl acrylate leveling agent is GLP588 and GLP701.
The moisture-heat resistant epoxy powder composition for the magnetic ring is applied to the packaging of electronic components.
The preparation method of the damp-heat resistant epoxy powder composition for the magnetic ring comprises the following steps of:
premixing various raw materials except the thixotropic agent in a high-speed mixer with the rotating speed of 500-1500rpm for 5-15 minutes, then adding the raw materials into a double-screw extruder, setting the temperature at 80-120 ℃, enabling the molten resin to be uniformly mixed with other raw materials under the shearing state of a screw, cooling the melt through a cooling press roller, enabling the cooled melt to enter an ACM mill for crushing, carrying out a winnowing process and screening, collecting particles with the required particle size, and finally adding the thixotropic agent to enable the powder to be fluidized and fluffy, thus obtaining the moisture-heat resistant epoxy powder composition for the magnetic ring.
The beneficial effects obtained by the invention are as follows:
1. the composition of the invention has the following advantages:
(1) The moisture resistance and the humidity resistance of the coating are improved by adding the organosilicon modified epoxy resin; (2) Uniformly mixing an adhesion promoter from the latitude of an organic matter by adding epoxy phosphate modified epoxy resin, uniformly mixing the adhesion promoter from the latitude of an inorganic matter by adding an aluminum polyphosphate substance, wherein the two phosphate substances have the functions of reacting a phosphorus hydroxyl group with a metal matrix to generate a phosphate ferric salt compound, and become one of the components of a phosphate film; further, the phosphate group forms a stronger chelation with the surface of the metal substrate, so that a complex is formed by the chelation with the multivalent metal, and the polymer is firmly connected to the metal substrate in a covalent bond mode, so that the phosphate monomer in the coating becomes a bridge between the polymer coating film and the metal substrate, and the adhesive force of the coating on the metal substrate is enhanced; the adhesion force formed by the chemical bond is not reduced by the influence of the humid environment. The specific principle is shown in literature materials of wetting property and adhesive force of bridge deck corrosion-resistant steel bar sintering epoxy powder coating (Kuruvila Varughese, building structure, volume 39, prop. 2009, 4 th month, P907-P908), and in dry environment, the total adhesive force of the coating is equal to the sum of contributions of all adhesive forces: i.e. mechanical adhesion, polar-polar action (intermolecular forces or van der waals forces) and chemical adhesion. But when water enters the coating, the polar-polar bonds that occur at the interface between the coating and the hydroxyl groups on the metal surface are redirected and directed towards water molecules. The polarity-polarity adhesion will be lost in the individual areas, with a consequent reduction in the overall adhesion. In a humid environment, only mechanical and chemical adhesion are active. Most of the polar-polar adhesion is expected to recover once the water leaves the substrate, but complete recovery appears to be unlikely due to water intrusion, a change in the physical state of the molecule.
(3) The silane coupling agent is added to improve the binding force between the inorganic filler and the inorganic flame retardant and the epoxy resin, and the binding force between the coating and the metal substrate is improved, but as described above, the technical means can only improve the dry state adhesive force because the adhesive force is intermolecular force (Van der Waals force).
The wet adhesion between the coating and the metal substrate is increased by increasing the moisture resistance of the coating, the dry adhesion between the coating and the metal substrate is increased, and the three aspects are synergistic, so that the moisture and heat resistance of the epoxy insulating powder is improved, and the epoxy insulating powder can pass through 85 ℃ and 85%1000h and does not separate from the magnetic ring.
2. According to the composition, through an inorganic flame retardant and a solid organic phosphorus flame retardant, and simultaneously by matching with melamine borate and nano layered zirconium phosphate (ZrP), a phosphorus-nitrogen-boron flame retardant system is constructed, and UL 94V-0 flame retardance of a 0.3mm thin coating can be realized, wherein the thickness of the coating is basically consistent with that of an actual coating of a magnetic ring. The nanometer layered zirconium phosphate can promote the formation of carbon and form a barrier layer during combustion, has better synergistic flame retardant effect, and can be peeled off in an organic system to endow the coating with excellent stress absorption capability.
3. The composition of the invention is coated with polyethylene micro wax powder, and imidazole which is not treated by masking agent, such as 2-methylimidazole (2 MZ), 2-phenylimidazole (2 PZ), 2-phenyl-4-methylimidazole (2P 4 MZ); or imidazole treated directly with a masking agent, for example; 2,4 '-diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine (2 MZ-A), 2,4' -diamino-6- [2 '-methylimidazolyl- (1') ] -ethyl-s-triazine isocyanuric acid adduct dehydrate (2 MA-OK), 1-cyanoethyl-2-phenylimidazolium-trimellitate (2 PZCNS), 2-phenyl-4, 5-dihydroxymethylimidazole (2 PHZ), etc., to improve the storage stability of the epoxy powder composition.
4. The epoxy powder composition can meet the halogen-free environment-friendly requirement (Cl is less than or equal to 900ppm, br is less than or equal to 900ppm, cl+Br is less than or equal to 1500 ppm), meets ROHS2.0, and belongs to an environment-friendly product.
5. The epoxy powder composition of the invention can be mainly used for insulating protection of magnetic rings (iron-silicon-aluminum, iron-based amorphous strips, iron powder cores, manganese cores, nickel cores and the like) made of various materials, and meets the process conditions of 190-230 ℃ preheating coating and 200 ℃/(5-10) minute curing. And the method can also be applied to insulation protection of electronic elements such as bus bars, rotors, stators, polymer fuses (PPTC) and the like.
6. The invention relates to a method for preparing a composite material, which is characterized in that on the basis of the inventor patent CN114015327B, wax powder modified imidazole and latent imidazole derivatives with masking agents are used, organosilicon modified epoxy resin is used for increasing hydrophobicity, phosphate modified epoxy resin is used for improving the adhesive force with a metal substrate, aluminum polyphosphate adhesive force promoter is used for improving the adhesive force with the metal substrate, silane coupling agent with active functional groups is used for improving the adhesive force between resin, filler and the metal substrate, nano layered zirconium phosphate is used for improving flame retardance and improving the impact resistance of the composite material, and the CN114015327B has obvious difference from the patent.
Detailed Description
The present invention will be further described in detail with reference to examples, but the scope of the present invention is not limited to the examples.
The raw materials used in the invention are conventional commercial products unless specified otherwise, the methods used in the invention are conventional methods in the art unless specified otherwise, and the mass of each substance used in the invention is conventional.
The moisture-heat resistant epoxy powder composition for the magnetic ring comprises the following components in parts by weight:
preferably, the epoxy resin 1 is a solid bisphenol a epoxy resin, and the softening point is: 60-130 ℃, the epoxy equivalent is: 450-1800g/eq;
or the epoxy resin 2 is solid organic silicon modified epoxy resin;
or the epoxy resin 3 is modified epoxy resin containing phosphate, and the specific preparation method comprises the following steps:
the epoxy phosphate resin prepared by reacting epoxy resin E44 with phosphoric acid has the following reaction formula:
3 parts by weight of epoxy phosphate resin is taken and added into 5 parts by weight of silicon micropowder in a dropwise manner, and the mixture is uniformly mixed by a high-speed mixer at 500-1500rpm for 5-15 minutes; then adding 10 parts by weight of CYD-014, NPES904 or GESR904, uniformly mixing by a high-speed mixer at 500-1500rpm for 5-15 minutes; and then the mixture is melted and extruded by a double-screw extruder, the temperature of the extruder is set to 120-130 ℃, the mixture is crushed by a crusher after being cooled by a cooling press roller, and the mixture is screened by a 100-target standard sieve, so that the epoxy resin 3 can be obtained.
Preferably, the epoxy resin 1 is E12, NPES907, NPES904, GESR903, CYD-014U, CYD-014 or CYD-012.
Preferably, the imidazole curing agent is: one or a mixture of imidazole curing agents without masking agent and imidazole curing agents with masking agent, which are coated by wax powder;
the preparation method of the imidazole curing agent without masking agent, which is coated by the wax powder, comprises the following steps:
uniformly mixing 1-2 parts by weight of polyethylene micro powder wax (melting point: 100-130 ℃) and 2-3 parts by weight of imidazole substances without masking agents, wherein the rotating speed is 500-1500rpm, and the mixing time is 5-15 minutes; then the mixture is melted and extruded by a double screw extruder, the temperature of the extruder is set to 120-140 ℃, the mixture is crushed by a crusher after being cooled by a cooling press roller, and the mixture is sieved by a 100-mesh standard sieve, so that the imidazole curing agent which is coated by wax powder and does not contain masking agent is obtained;
the imidazole curing agent with masking agent comprises: 1-cyanoethyl-2-undecylimidazolium-trimellitate (C11Z-CNS), 1-cyanoethyl-2-phenylimidazolium-trimellitate (2 PZCNS), 1-cyanoethyl-2-phenylimidazolium-trimellitate micropowder (2 PZCNS-PW), 2,4' -diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine (2 MZ-A), 2,4' -diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine micropowder (2 MZA-PW), 2,4' -diamino-6- [2' -ethyl-4 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine (2E 4 MZ-A), 2,4' -diamino-6- [2' -undecylimidazolyl- (1 ') ] -ethyl-s-triazine (C11Z-A); 2-phenylimidazole isocyanuric acid adduct (2 PZ-OK), 2,4' -diamino-6- [2' -methylimidazole- (1 ') ] -ethyl-s-triazine isocyanuric acid adduct dehydrate (2 MA-OK), 2-phenyl-4, 5-dihydroxymethylimidazole (2 PHZ), 2-phenyl-4, 5-dihydroxymethylimidazole micropowder (2 PHZ-PW), 2-phenyl-4-methyl-5-hydroxymethylimidazole (2P 4 MHZ), 2-phenyl-4-methyl-5-hydroxymethylimidazole micropowder (2P 4 MHZ-PW).
Preferably, the imidazole-based material without masking agent is 2-methylimidazole (2 MZ), or 2-phenylimidazole (2 PZ), or 2-phenyl-4-methylimidazole (2P 4 MZ).
Preferably, the filler is one or a combination of more than two of silicon micropowder, talcum powder, mica powder, calcium silicate, zirconium silicate, calcium carbonate, barium sulfate and kaolin;
or the inorganic flame retardant is one or a combination of more than two of aluminum hydroxide, magnesium hydroxide, boehmite and carbonate type aluminum-magnesium hydrotalcite;
or the solid organic phosphorus flame retardant is one or a combination of more than two of solid phosphazenes and solid phosphates;
or, the melamine borate is a synergistic flame retardant;
or the zirconium phosphate flame retardant is one or a combination of two of zirconium phosphate and organically modified zirconium phosphate.
Preferably, the adhesion promoter 1 is one or a combination of two or more of aluminum tripolyphosphate, modified aluminum tripolyphosphate and aluminum dihydrogen tripolyphosphate;
or the adhesion promoter 2 is one or a combination of two or more of amino-type organosiloxane, epoxy-type organosiloxane and mercapto-type organosiloxane;
or the titanium dioxide is one or a combination of two of rutile titanium dioxide and anatase titanium dioxide;
or the pigment is one or a combination of two or more of phthalocyanine blue, iron red, iron yellow, organic yellow pigment, organic red pigment, organic orange pigment, carbon black and inorganic black pigment;
or the leveling agent is polybutyl acrylate leveling agent;
or the degasifying agent is one or two of benzoin and modified benzoin;
or the externally added thixotropic agent is one or a combination of two of fumed silica and fumed alumina;
preferably, the amino-type organosiloxane is KH540, the epoxy-type organosiloxane is KH60, and the mercapto-type organosiloxane is KH590; the polybutyl acrylate leveling agent is GLP588 and GLP701.
The moisture-heat resistant epoxy powder composition for the magnetic ring is applied to the packaging of electronic components.
The preparation method of the damp-heat resistant epoxy powder composition for the magnetic ring comprises the following steps of:
premixing various raw materials except the thixotropic agent in a high-speed mixer with the rotating speed of 500-1500rpm for 5-15 minutes, then adding the raw materials into a double-screw extruder, setting the temperature at 80-120 ℃, enabling the molten resin to be uniformly mixed with other raw materials under the shearing state of a screw, cooling the melt through a cooling press roller, enabling the cooled melt to enter an ACM mill for crushing, carrying out a winnowing process and screening, collecting particles with the required particle size, and finally adding the thixotropic agent to enable the powder to be fluidized and fluffy, thus obtaining the moisture-heat resistant epoxy powder composition for the magnetic ring.
Specifically, the preparation and detection of the correlation are as follows:
the epoxy resin 3 is synthesized, for example, as follows (the unit of the formula is weight part):
synthesis example 1:
3 parts of epoxy phosphate resin is taken and added into 5 parts of silicon micropowder in a dropwise manner, and the mixture is uniformly mixed by a high-speed mixer at the rotating speed of 500-1500rpm for 5-15 minutes; then adding 10 parts of CYD-014, uniformly mixing by a high-speed mixer at 500-1500rpm for 5-15 minutes; and then the mixture is melted and extruded by a double-screw extruder, the temperature of the extruder is set to 130 ℃, the mixture is crushed by a crusher after being cooled by a cooling press roll, and the mixture is screened by a 100-target standard sieve, so that the epoxy resin 3 phosphate-containing modified epoxy resin can be obtained.
Specific polyethylene micropowder waxes imidazole curing agents without masking agents are synthesized, for example, as follows (the unit of the formulation is parts by weight):
synthesis example 2: mixing 1 part of polyethylene micro powder wax and 1 part of 2-methylimidazole, uniformly mixing by a small high-speed mixer at 500-1500rpm for 5-15 minutes. And then the mixture is melted and extruded by a double-screw extruder, the temperature of the extruder is set to 130 ℃, the mixture is crushed by a crusher after being cooled by a cooling press roll, and the mixture is screened by a 100-target standard sieve, so that the polyethylene wax coated 2-methylimidazole can be obtained.
Synthesis example 3: mixing 1 part of polyethylene micro powder wax and 1 part of 2-phenylimidazole, uniformly mixing by a small high-speed mixer at 500-1500rpm for 5-15 minutes. And then the mixture is melted and extruded by a double-screw extruder, the temperature of the extruder is set to 130 ℃, the mixture is crushed by a crusher after being cooled by a cooling press roll, and the mixture is screened by a 100-target standard sieve, so that the polyethylene wax coated 2-phenylimidazole can be obtained.
Synthesis example 4: mixing 1 part of polyethylene micro powder wax and 1 part of 2-phenyl-4-methylimidazole, uniformly mixing by a small high-speed mixer at 500-1500rpm for 5-15 minutes. And then the mixture is melted and extruded by a double screw extruder, the temperature of the extruder is set to 130 ℃, the mixture is crushed by a crusher after being cooled by a cooling press roll, and the mixture is screened by a 100-target standard sieve, so that the polyethylene wax coated 2-phenyl-4-methylimidazole can be obtained.
Specific examples, comparative examples and related test results are shown below (formula unit in parts by weight):
comparative example 1
The powder composition for the magnetic ring comprises the following components in parts by weight:
the manufacturing method comprises the following steps: premixing other raw materials except the thixotropic agent in a high-speed mixer with the rotating speed of 500-1500rpm for 5-15 minutes, then adding the mixture into a double-screw extruder, setting the temperature at 80-120 ℃, enabling the molten resin to be mixed with other raw materials uniformly under the shearing state of a screw, cooling the melt through a cooling compression roller, grinding and crushing the cooled melt by an ACM mill, collecting particles with the required particle size through a winnowing process and screening, and finally adding the thixotropic agent to enable the powder to be fluidized and fluffy, thus obtaining the moisture-heat resistant epoxy powder composition for the magnetic ring.
Comparative example 2
The powder composition for the magnetic ring comprises the following components in parts by weight:
the manufacturing method is the same as that of comparative example 1.
Comparative example 3
The powder composition for the magnetic ring comprises the following components in parts by weight:
the manufacturing method is the same as that of comparative example 1.
Comparative example 4
The powder composition for the magnetic ring comprises the following components in parts by weight:
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the manufacturing method is the same as that of comparative example 1.
Comparative example 5
The powder composition for the magnetic ring comprises the following components in parts by weight:
the manufacturing method is the same as that of comparative example 1.
Comparative example 6
The powder composition for the magnetic ring comprises the following components in parts by weight:
the manufacturing method is the same as that of comparative example 1.
Comparative example 7
The powder composition for the magnetic ring comprises the following components in parts by weight:
the manufacturing method is the same as that of comparative example 1.
Comparative example 8
The powder composition for the magnetic ring comprises the following components in parts by weight:
the manufacturing method is the same as that of comparative example 1.
Comparative example 9
The powder composition for the magnetic ring comprises the following components in parts by weight:
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the manufacturing method is the same as that of comparative example 1.
Comparative example 10
The powder composition for the magnetic ring comprises the following components in parts by weight:
the manufacturing method is the same as that of comparative example 1.
Example 1
The moisture-heat resistant epoxy powder composition for the magnetic ring comprises the following components in parts by weight:
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the manufacturing method is the same as that of comparative example 1.
Example 2
The moisture-heat resistant epoxy powder composition for the magnetic ring comprises the following components in parts by weight:
the manufacturing method is the same as that of comparative example 1.
Example 3
The moisture-heat resistant epoxy powder composition (for electrostatic spraying) for the magnetic ring comprises the following components in parts by weight:
the manufacturing method is the same as that of comparative example 1. The particle size distribution is different from example 2, which is suitable for electrostatic spraying process.
Example 4
The moisture-heat resistant epoxy powder composition for the magnetic ring comprises the following components in parts by weight:
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the manufacturing method is the same as that of comparative example 1.
Example 5
The moisture-heat resistant epoxy powder composition for the magnetic ring comprises the following components in parts by weight:
the manufacturing method is the same as that of comparative example 1.
Example 6
The moisture-heat resistant epoxy powder composition for the magnetic ring comprises the following components in parts by weight:
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the manufacturing method is the same as that of comparative example 1.
Example 7
The moisture-heat resistant epoxy powder composition for the magnetic ring comprises the following components in parts by weight:
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the manufacturing method is the same as that of comparative example 1.
The test results were as follows:
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the invention relates to a test item and a method thereof:
in order to verify the beneficial effects of the invention, the relevant item test is performed:
(1) Powder characteristics: horizontal flow rate, gel time, 45 micron laser particle size, roll;
(2) Cured product characteristics: after curing at 200 ℃/5 minutes
(1) Flame retardancy: UL94 vertical burn test, flame retardant rating.
(2) Double 85 test of magnetic ring
(3) Adhesion force
(4) Electrical strength of
(3) Environmental protection substances: chlorine (Cl), bromine (Br), rohs2.0 test program.
Some performance index testing methods in the invention are as follows:
(1) Horizontal flow rate: according to 5.1.6 in GB/T28859-2012 epoxy powder packaging material for electronic components, the temperature is set to 150+/-2 ℃ and the holding time is 30min.
(2) Gel time: according to the method of GB/16995-1997 determination of the gel time of a thermosetting powder coating at a given temperature, the temperature is set at 160.+ -. 2 ℃.
(3) 45 micron laser granularity, according to GBT19077-2016 particle size distribution laser diffraction method,
(4) Roll-ability: 40g of powder was weighed using a Buchner funnel, and an air flow meter was used to control the flow rate, 0.05m 3 /h。
(5) Flame retardancy: according to UL94, vertical burn test. Thickness 1.0mm test: 127 x 12.7 x 1mm rectangular bars, 5pcs per group. Thickness 0.3mm test: 127 x 12.7 x 0.3mm rectangular bars, 5pcs per group.
(6) Magnetic ring double 85 test: the magnetic ring is coated by a roll coating method for roll coating powder, the magnetic ring is coated by an electrostatic spraying method for electrostatic spraying powder, the single layer thickness of the coating is about 0.3mm, and each group of the coating is 5pcs according to STRESS TEST QUALIFICATION FOR PASSIVE COMPONENTS. And (3) placing the sample in a temperature and humidity box with 85 ℃ and 85% humidity, observing and recording whether the coating and the magnetic ring are separated or not at different time, and judging whether the coating is qualified after 1000 hours without swelling.
(7) Adhesion force: according to GB/T9286-1998, cross-hatch test of color and varnish films.
(8) Electrical strength: according to GB/T1408.1-2016 test under the power frequency of the 1 st part of the test method for the electric strength of insulating materials, test samples with the diameter of about 100mm and the thickness of about 0.5mm are pressed in a die, and each group is 5pcs. The cured samples were tested for electrical strength in insulating oil.
(9) Environmental protection substances:
(1) chlorine (Cl), bromine (Br) according to IEC 61249-2-21.
(2) RoHS2.0 test item, in accordance with RoHS2.0.
The invention has the beneficial effects that:
1. comparison of example 2 with comparative examples 1, 2 and 3 shows that the phenolic hydroxyl resin curing system, dicyandiamide curing system and 2-methylimidazole curing system do not meet the requirements of double 85 tests when epoxy resins 2 and 3 and adhesion promoters 1 and 2 are not added. In contrast, the double 85 test, the 2-methylimidazole curing system is superior to the dicyandiamide curing system to the phenolic resin curing system because the composite curing agent interferes with the curability of the imidazoles, but rather cannot achieve a higher degree of crosslinking, and thus has poor resistance to moisture.
2. Comparison of example 2 and comparative example 4 shows that the addition of epoxy resin 3 can improve the adhesive force after the magnetic ring double-85 test and improve the wet heat resistance, and the main reason is that the phosphate substance has the function of reacting the phosphorus hydroxyl group with the metal matrix to generate a phosphate ferric salt compound which becomes one of the components of the phosphating film; further, the phosphorus hydroxyl group forms a strong chelation with the surface of the metal substrate, thereby forming a complex with the polyvalent metal, and firmly connecting the polymer to the metal substrate in a covalent bond mode.
3. Comparison of example 2 with comparative example 5 shows that epoxy resin 3 and adhesion promoter 1, and epoxy resin 3 and adhesion promoter 1 can cooperate to significantly improve adhesion after magnetic ring double 85 test to improve wet heat resistance, for the same reasons as described above.
4. Example 2 and comparative examples 5, 6, 7 demonstrate that the addition of epoxy 2 and adhesion promoter 2, also synergistically enhance the double 85 test capability of the magnetic ring to some extent. The reason is that the organosilicon modified epoxy resin improves the hydrophobicity of the coating because the molecular chain segment of the organosilicon modified epoxy resin contains hydrophobic organosilicon chain segments. The KH560 silane coupling agent improves the adhesion between the resin and the inorganic and metallic substrates in the dry state, and the main form is intermolecular force (Van der Waals force) which is reduced after moisture enters, so that the silane coupling agent KH560 does not significantly improve the moist heat resistance of the magnetic ring.
Meanwhile, as can be seen from the embodiment 2 and the comparative examples 1 to 10, the powder composition of the invention has a synergistic effect among the components of the epoxy resin 1, the epoxy resin 2 and the epoxy resin 3, and can synergistically improve the adhesive force after the magnetic ring double-85 test and improve the wet heat resistance.
5. Comparison of example 2 with comparative examples 8, 9 and 10 shows that the inorganic flame retardant and the solid organic phosphorus flame retardant have a synergistic effect, and can synergistically realize UL 94V-0 flame retardance with a thickness of 1.0mm, but can only reach V-1 when the coating is thinned to a thickness of 0.3 mm. As zirconium phosphate or melamine borate continues to be added, the UL94 flame retardancy at a thickness of 0.3mm is slightly improved by approximately V-0. When zirconium phosphate and melamine borate are added simultaneously, the UL94 flame retardance of 0.3mm thickness reaches V-0. The main reason is that after melamine borate is added on the basis of inorganic flame retardant and solid organic phosphorus flame retardant, the flame retardance is improved by utilizing the synergism of phosphorus, nitrogen and boron, and the flame retardance is further improved by utilizing the barrier effect of the protective film formed by catalyzing carbon formation of zirconium phosphate, so that the V-0 flame retardance level of a 0.3mm thin coating is achieved. The actual thickness of the coating after the coating of the magnetic ring is basically 0.3 mm.
6. Imidazoles such as 2-methylimidazole (2 MZ) and 2-phenylimidazole (2 PZ) which have not been treated with a masking agent have poor storage stability, and thus it is required to improve the storage life after being coated with polyethylene micro wax powder.
7. Imidazole treated with masking agents, such as 2,4 '-diamino-6- [2' -ethyl-4 '-methylimidazolyl- (1') ] -ethyl-s-triazine (2E 4 MZ-A), 2,4 '-diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine (2 MZ-A), 2,4' -diamino-6- [2 '-methylimidazolyl- (1') ] -ethyl-s-triazine isocyanuric acid adduct dehydrate (2 MA-OK), 1-cyanoethyl-2-phenylimidazolium-trimellitate (2 PZCNS), 2-phenyl-4, 5-dihydroxymethylimidazole (2 PHZ), have a longer shelf life by themselves and require higher addition amounts for obtaining higher reaction rates.
Through the technical means, the invention realizes excellent wet heat resistance after the magnetic ring is coated, meets the double 85 test requirements, has excellent electrical insulation and process usability, meets the 0.3mm thin layer UL 94V-0 level flame retardance, meets the halogen-free requirement and the RoHS2.0 environment-friendly requirement, has high market application value and prospect, and is worthy of further popularization and application.
Although embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that: various substitutions, changes and modifications are possible without departing from the spirit and scope of the invention and the appended claims, and therefore the scope of the invention is not limited to the disclosure of the embodiments.
Claims (8)
1. A wet heat resistant epoxy powder composition for magnetic rings is characterized in that: the components and parts by weight thereof are as follows:
the epoxy resin 1 is solid bisphenol A type epoxy resin, and the softening point is as follows: 60-130 ℃, the epoxy equivalent is: 450-1800g/eq;
the epoxy resin 2 is solid organic silicon modified epoxy resin;
the epoxy resin 3 is modified epoxy resin containing phosphate, and the specific preparation method comprises the following steps:
the epoxy phosphate resin prepared by reacting epoxy resin E44 with phosphoric acid has the following reaction formula:
3 parts by weight of epoxy phosphate resin is taken and added into 5 parts by weight of silicon micropowder in a dropwise manner, and the mixture is uniformly mixed by a high-speed mixer at 500-1500rpm for 5-15 minutes; then adding 10 parts by weight of CYD-014, NPES904 or GESR904, uniformly mixing by a high-speed mixer at 500-1500rpm for 5-15 minutes; then the mixture is melted and extruded by a double screw extruder, the temperature of the extruder is set to 120-130 ℃, the mixture is crushed by a crusher after being cooled by a cooling press roll, and the mixture is screened by a 100-target standard sieve, so that the epoxy resin 3 can be obtained;
the imidazole curing agent is as follows: one or a mixture of imidazole curing agents without masking agent and imidazole curing agents with masking agent, which are coated by wax powder;
the preparation method of the imidazole curing agent without masking agent, which is coated by the wax powder, comprises the following steps:
1-2 parts by weight of polyethylene micro powder wax, and the melting point: mixing 100-130deg.C with 2-3 parts by weight of imidazole substance without masking agent, rotating at 500-1500rpm for 5-15 min; then the mixture is melted and extruded by a double screw extruder, the temperature of the extruder is set to 120-140 ℃, the mixture is crushed by a crusher after being cooled by a cooling press roller, and the mixture is sieved by a 100-mesh standard sieve, so that the imidazole curing agent which is coated by wax powder and does not contain masking agent is obtained;
the imidazole curing agent with masking agent comprises: 1-cyanoethyl-2-undecylimidazolium-trimellitate, 1-cyanoethyl-2-phenylimidazolium-trimellitate micropowder, 2,4 '-diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine micropowder, 2,4' -diamino-6- [2 '-ethyl-4' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2,4' -diamino-6- [2 '-undecylimidazolyl- (1') ] -ethyl-s-triazine; 2-phenylimidazole isocyanuric acid adduct, 2,4' -diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine isocyanuric acid adduct dehydrate, 2-phenyl-4, 5-dihydroxymethylimidazole micropowder, 2-phenyl-4-methyl-5-hydroxymethylimidazole micropowder.
2. The moisture-heat resistant epoxy powder composition for a magnetic ring as set forth in claim 1, wherein: the epoxy resin 1 is E12, NPES907, NPES904, GESR903, CYD-014U, CYD-014 or CYD-012.
3. The moisture-heat resistant epoxy powder composition for a magnetic ring as set forth in claim 1, wherein: the imidazole substance without masking agent is 2-methylimidazole, or 2-phenylimidazole, or 2-phenyl-4-methylimidazole.
4. The moisture-heat resistant epoxy powder composition for a magnetic ring as set forth in claim 1, wherein: the filler is one or a combination of two or more of silicon micropowder, talcum powder, mica powder, calcium silicate, zirconium silicate, calcium carbonate, barium sulfate and kaolin;
or the inorganic flame retardant is one or a combination of more than two of aluminum hydroxide, magnesium hydroxide, boehmite and carbonate type aluminum-magnesium hydrotalcite;
or the solid organic phosphorus flame retardant is one or a combination of more than two of solid phosphazenes and solid phosphates;
or, the melamine borate is a synergistic flame retardant;
or the zirconium phosphate flame retardant is one or a combination of two of zirconium phosphate and organically modified zirconium phosphate.
5. The moisture-heat resistant epoxy powder composition for a magnetic ring as set forth in claim 1, wherein: the adhesion promoter 1 is one or a combination of more than two of aluminum tripolyphosphate, modified aluminum tripolyphosphate and aluminum dihydrogen tripolyphosphate;
or the adhesion promoter 2 is one or a combination of two or more of amino-type organosiloxane, epoxy-type organosiloxane and mercapto-type organosiloxane;
or the titanium dioxide is one or a combination of two of rutile titanium dioxide and anatase titanium dioxide;
or the pigment is one or a combination of two or more of phthalocyanine blue, iron red, iron yellow, organic yellow pigment, organic red pigment, organic orange pigment, carbon black and inorganic black pigment;
or the leveling agent is polybutyl acrylate leveling agent;
or the degasifying agent is one or two of benzoin and modified benzoin;
or the externally added thixotropic agent is one or a combination of two of fumed silica and fumed alumina.
6. The moisture-heat resistant epoxy powder composition for a magnetic ring as defined in claim 5, wherein: the amino-type organosiloxane is KH540, the epoxy-type organosiloxane is KH60, and the mercapto-type organosiloxane is KH590; the polybutyl acrylate leveling agent is GLP588 and GLP701.
7. Use of the moisture and heat resistant epoxy powder composition for magnetic rings as defined in any one of claims 1 to 6 in packaging of electronic components.
8. A method for preparing the moisture-heat resistant epoxy powder composition for a magnetic ring as set forth in any one of claims 1 to 6, characterized in that: the method comprises the following steps:
premixing various raw materials except the thixotropic agent in a high-speed mixer with the rotating speed of 500-1500rpm for 5-15 minutes, then adding the raw materials into a double-screw extruder, setting the temperature at 80-120 ℃, enabling the molten resin to be uniformly mixed with other raw materials under the shearing state of a screw, cooling the melt through a cooling press roller, enabling the cooled melt to enter an ACM mill for crushing, carrying out a winnowing process and screening, collecting particles with the required particle size, and finally adding the thixotropic agent to enable the powder to be fluidized and fluffy, thus obtaining the moisture-heat resistant epoxy powder composition for the magnetic ring.
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